TW202302450A - Graphene conductive film and manufacturing method thereof, graphene- carbon nanotube conductive film and manufacturing method thereof - Google Patents
Graphene conductive film and manufacturing method thereof, graphene- carbon nanotube conductive film and manufacturing method thereof Download PDFInfo
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本發明為關於導電薄膜，特別是，一種利用網印塗佈和熱退火程序使石墨烯薄膜和石墨烯-奈米碳管導電薄膜的片電阻下降之石墨烯導電薄膜之製備方法及其石墨烯導電薄膜、石墨烯-奈米碳管導電薄膜之製備方法及其石墨烯-奈米碳管導電薄膜。The present invention relates to conductive films, in particular, a method for preparing graphene conductive films and graphene conductive films that utilize screen printing coating and thermal annealing procedures to reduce the sheet resistance of graphene films and graphene-carbon nanotube conductive films. Conductive thin film, preparation method of graphene-carbon nanotube conductive thin film and graphene-carbon nanotube conductive thin film.
近來，導電漿料的應用相當廣泛，例如印刷電路板、太陽能電池或發光二極體。石墨烯是一種導電性良浩且相當堅固的材料，石墨烯的顏色為透明，相當適合應用於消費性電子產品中，但現今的石墨烯的製造程序相當複雜且無法製造出大面積、平整且導電性良好的薄膜，因此石墨烯薄膜仍就處於開發階段而難以量產。Recently, conductive pastes are widely used in applications such as printed circuit boards, solar cells or light emitting diodes. Graphene is a highly conductive and very strong material. The color of graphene is transparent, which is quite suitable for use in consumer electronics products. However, the current manufacturing process of graphene is quite complicated and cannot produce large-area, flat and conductive materials. Therefore, graphene films are still in the development stage and difficult to mass-produce.
綜觀前所述，本發明之發明者思索並設計一種石墨烯導電薄膜之製備方法及其石墨烯導電薄膜、石墨烯-奈米碳管導電薄膜之製備方法及其石墨烯-奈米碳管導電薄膜，以期針對習知技術之缺失加以改善，進而增進產業上之實施利用。In view of the foregoing, the inventors of the present invention contemplate and design a method for preparing a graphene conductive film, a method for preparing a graphene conductive film, a method for preparing a graphene-carbon nanotube conductive film, and a graphene-carbon nanotube conductive film. Thin film, in order to improve the deficiencies of conventional technology, and then enhance the implementation and utilization in industry.
基於上述目的，本發明提供一種石墨烯導電薄膜之製備方法及其石墨烯導電薄膜、石墨烯-奈米碳管導電薄膜之製備方法及其石墨烯-奈米碳管導電薄膜，用以解決習知技術中所面臨之問題。Based on above-mentioned purpose, the present invention provides a kind of preparation method of graphene conductive film and its graphene conductive film, the preparation method of graphene-carbon nanotube conductive film and its graphene-carbon nanotube conductive film, in order to solve conventional Know the problems faced by the technology.
基於上述目的，本發明提供一種石墨烯導電薄膜之製備方法，其包括：(1)調配石墨烯、界面活性劑和溶劑。(2) 混合石墨烯、界面活性劑和溶劑為石墨烯導電漿料。(3) 網印塗佈石墨烯導電漿料於基板，形成石墨烯導電薄膜於基板上。(4)乾燥石墨烯導電薄膜。(4) 熱退火石墨烯導電薄膜。Based on the above purpose, the present invention provides a method for preparing a graphene conductive film, which includes: (1) preparing graphene, a surfactant and a solvent. (2) Mix graphene, surfactant and solvent to be graphene conductive paste. (3) Apply graphene conductive paste to the substrate by screen printing to form a graphene conductive film on the substrate. (4) dry graphene conductive film. (4) Thermally annealed graphene conductive film.
可選地，於調配石墨烯、界面活性劑和溶劑的步驟前，乾燥石墨烯。Optionally, the graphene is dried before the step of preparing the graphene, surfactant and solvent.
基於上述目的，本發明提供一種石墨烯-奈米碳管導電薄膜之製備方法，其包括：(1)調配奈米碳管、石墨烯、界面活性劑和溶劑。(2)混合奈米碳管、石墨烯、界面活性劑和溶劑為石墨烯-奈米碳管導電漿料。(3)網印塗佈石墨烯-奈米碳管導電漿料於基板，形成石墨烯-奈米碳管導電薄膜於基板上。(4)乾燥石墨烯-奈米碳管導電薄膜。(5)熱退火石墨烯-奈米碳管導電薄膜Based on the above purpose, the present invention provides a method for preparing a graphene-carbon nanotube conductive film, which includes: (1) preparing carbon nanotubes, graphene, a surfactant and a solvent. (2) mixing carbon nanotubes, graphene, a surfactant and a solvent to be a graphene-carbon nanotube conductive paste. (3) Coating the graphene-carbon nanotube conductive paste on the substrate by screen printing to form a graphene-carbon nanotube conductive film on the substrate. (4) drying the graphene-carbon nanotube conductive film. (5) Thermally annealed graphene-carbon nanotube conductive film
可選地，於調配奈米碳管、石墨烯、界面活性劑和溶劑的步驟前，執行純化程序於奈米碳管。Optionally, a purification procedure is performed on the carbon nanotubes before the step of preparing the carbon nanotubes, graphene, surfactant and solvent.
一種石墨烯導電薄膜，利用前述石墨烯導電薄膜之製備方法所製，其中石墨烯的重量百分濃度為1-4重量%，界面活性劑的重量百分濃度為1-5重量%。A graphene conductive film made by the aforementioned method for preparing a graphene conductive film, wherein the weight percent concentration of graphene is 1-4% by weight, and the weight percent concentration of surfactant is 1-5% by weight.
可選地，石墨烯導電薄膜之片電阻值為介於20至2600歐姆/sq的範圍。Optionally, the sheet resistance of the graphene conductive film ranges from 20 to 2600 ohms/sq.
一種石墨烯-奈米碳管導電薄膜，利用前述石墨烯-奈米碳管導電薄膜之製備方法所製，其中石墨烯的重量百分濃度為1-4重量%，奈米碳管的重量百分濃度為0~0.5重量%，界面活性劑的重量百分濃度為1-5重量%。A graphene-carbon nanotube conductive film, made by the above-mentioned graphene-carbon nanotube conductive film preparation method, wherein the weight percent concentration of graphene is 1-4% by weight, and the weight percentage of carbon nanotube is 100%. The concentration is 0-0.5% by weight, and the concentration by weight of the surfactant is 1-5% by weight.
可選地，石墨烯-奈米碳管導電薄膜之片電阻值為介於10至30歐姆/sq的範圍。Optionally, the sheet resistance of the graphene-carbon nanotube conductive film ranges from 10 to 30 ohms/sq.
承上所述，本發明之石墨烯導電薄膜和其製備方法，利用界面活性劑的添加和乾燥、熱退火製程的搭配，使石墨烯導電薄膜的片電阻下降而導電率提高。Based on the above, the graphene conductive film and its preparation method of the present invention use the addition of surfactants and the combination of drying and thermal annealing processes to reduce the sheet resistance of the graphene conductive film and increase the conductivity.
承上所述，本發明之石墨烯-奈米碳管導電薄膜，利用界面活性劑和奈米碳管的添加和乾燥、熱退火製程的搭配，使石墨烯-奈米碳管導電薄膜的片電阻下降而導電率提高，且製備方法容易，而能應用於低成本電子元件。As mentioned above, the graphene-carbon nanotube conductive film of the present invention utilizes the addition of surfactant and carbon nanotube and the combination of drying and thermal annealing process to make the sheet of graphene-carbon nanotube conductive film The resistance decreases while the conductivity increases, and the preparation method is easy, so it can be applied to low-cost electronic components.
本發明之優點、特徵以及達到之技術方法將參照例示性實施例及所附圖式進行更詳細地描述而更容易理解，且本發明可以不同形式來實現，故不應被理解僅限於此處所陳述的實施例，相反地，對所屬技術領域具有通常知識者而言，所提供的實施例將使本揭露更加透徹與全面且完整地傳達本發明的範疇，且本發明將僅為所附加的申請專利範圍所定義。The advantages, features and technical methods achieved by the present invention will be described in more detail with reference to exemplary embodiments and accompanying drawings to make it easier to understand, and the present invention can be implemented in different forms, so it should not be understood as being limited to what is shown here The stated embodiments, on the contrary, for those skilled in the art, the provided embodiments will make the present disclosure more thorough and comprehensive and completely convey the scope of the present invention, and the present invention will be only the appended The scope of the patent application is defined.
另外，術語「包括」及/或「包含」指所述特徵、區域、整體、步驟、操作、元件及/或部件的存在，但不排除一個或多個其他特徵、區域、整體、步驟、操作、元件、部件及/或其組合的存在或添加。In addition, the terms "comprising" and/or "comprising" refer to the presence of stated features, regions, integers, steps, operations, elements and/or parts, but do not exclude one or more other features, regions, integers, steps, operations , the presence or addition of elements, parts and/or combinations thereof.
除非另有定義，本發明所使用的所有術語(包括技術和科學術語)具有與本發明所屬技術領域的普通技術人員通常理解的相同含義。將進一步理解的是，諸如在通常使用的字典中定義的那些術語應當被解釋為具有與它們在相關技術和本發明的上下文中的含義一致的定義，並且將不被解釋為理想化或過度正式的意義，除非本文中明確地這樣定義。Unless otherwise defined, all terms (including technical and scientific terms) used in this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. It will be further understood that terms such as those defined in commonly used dictionaries should be interpreted to have definitions consistent with their meanings in the context of the relevant art and the present invention, and will not be interpreted as idealistic or overly formal unless otherwise expressly defined herein.
請參閱第1圖，其為本發明之石墨烯導電薄膜的製造流程圖。如第1圖所示，本發明之石墨烯導電薄膜的製造流程如下：S11步驟：利用烘箱對石墨烯以溫度100度並持續24小時進行乾燥，去除石墨烯的水分。Please refer to Fig. 1, which is a manufacturing flow chart of the graphene conductive film of the present invention. As shown in Figure 1, the manufacturing process of the graphene conductive film of the present invention is as follows: Step S11: Use an oven to dry the graphene at a temperature of 100 degrees for 24 hours to remove the moisture in the graphene.
S12步驟：調配石墨烯、界面活性劑和溶劑；舉例來說，石墨烯可為0.1g-0.4g，界面活性劑可為聚乙烯吡咯烷酮(Polyvinylpyrrolidone, PVP)而其為1-5重量%，溶劑可為乙二醇。S12 step: deploy graphene, surfactant and solvent; For example, graphene can be 0.1g-0.4g, surfactant can be polyvinylpyrrolidone (Polyvinylpyrrolidone, PVP) and it is 1-5% by weight, solvent It can be ethylene glycol.
S13步驟：利用磁石攪拌機攪拌並混合石墨烯、界面活性劑和溶劑為石墨烯導電漿料。Step S13: using a magnetic stirrer to stir and mix the graphene, the surfactant and the solvent to form the graphene conductive paste.
S14步驟：將基板放置於網版印刷機上，將網版對準於基板上，接著利用刮刀取石墨烯導電漿料並將其塗佈於網板上，使石墨烯導電漿料附著於基板上，改變網印速度，例如以50-100mm/sec的速度網印石墨烯導電漿料1-10次，形成石墨烯導電薄膜於基板上。Step S14: place the substrate on the screen printing machine, align the screen on the substrate, then use a scraper to take the graphene conductive paste and apply it on the screen, so that the graphene conductive paste adheres to the substrate Above, change the screen printing speed, for example, screen print the graphene conductive paste at a speed of 50-100mm/sec for 1-10 times to form a graphene conductive film on the substrate.
其中，基板可包括矽基板、藍寶石基板或碳化矽基板，當然其也可為其他類型的基板，而未侷限於本發明所列舉的範圍。網版的目數可例如為400目，當然其也可根據所需而有所變更，而未侷限於本發明所列舉的範圍。Wherein, the substrate may include a silicon substrate, a sapphire substrate or a silicon carbide substrate, of course, it may also be other types of substrates, and is not limited to the scope of the present invention. The mesh number of the screen can be, for example, 400 meshes, of course, it can also be changed according to needs, and is not limited to the scope listed in the present invention.
S15步驟：將具有石墨烯導電薄膜的基板，利用烘箱對石墨烯導電薄膜以80-100度並持續20-30分鐘進行乾燥。Step S15: drying the graphene conductive film on the substrate with the graphene conductive film in an oven at 80-100 degrees for 20-30 minutes.
S16步驟：乾燥後石墨烯導電薄膜，利用高溫爐對石墨烯導電薄膜以350-400度並持續30分鐘進行熱退火。Step S16: After drying the graphene conductive film, perform thermal annealing on the graphene conductive film at 350-400 degrees for 30 minutes in a high-temperature furnace.
利用本發明之石墨烯導電薄膜製備方法所製的石墨烯導電薄膜，石墨烯的重量百分濃度為1-4重量%，界面活性劑的重量百分濃度為1-5重量%。對石墨烯1重量%、2重量%、3重量%和4重量%的石墨烯導電薄膜的進行導電性量測，霍爾效應量測儀對不同重量百分濃度的石墨烯導電薄膜的電阻量測如下表1所示：
請參閱第2圖，其為本發明之石墨烯導電薄膜的掃描式電子顯微鏡的影像。如第2圖所示，a部分對應石墨烯1重量%的石墨烯導電薄膜，b部分對應石墨烯2重量%的石墨烯導電薄膜，c部分對應石墨烯3重量%的石墨烯導電薄膜，d部分對應石墨烯4重量%的石墨烯導電薄膜。如a部分所示，並搭配表1，石墨烯導電薄膜仍為層狀而無連續性，由於石墨烯導電薄膜並未形成完整的薄膜，相應地，石墨烯1重量%的石墨烯導電薄膜的片電阻遠比石墨烯2重量%、3重量%和4重量%的石墨烯導電薄膜來得大。如b部分所示，並搭配表1，石墨烯導電薄膜的石墨片開始部分連接，相應地，石墨烯2重量%的石墨烯導電薄膜的片電阻遠比石墨烯1重量%的石墨烯導電薄膜來得小。Please refer to FIG. 2, which is a scanning electron microscope image of the graphene conductive film of the present invention. As shown in Figure 2, part a corresponds to a graphene conductive film with 1% by weight of graphene, part b corresponds to a graphene conductive film with 2% by weight of graphene, part c corresponds to a graphene conductive film with 3% by weight of graphene, and d A graphene conductive film corresponding to 4% by weight of graphene. As shown in part a, and with table 1, the graphene conductive film is still layered without continuity, because the graphene conductive film does not form a complete film, correspondingly, the graphene conductive film of 1% by weight of graphene The sheet resistance is much larger than that of graphene conductive films with 2 wt%, 3 wt% and 4 wt% of graphene. As shown in part b, and with Table 1, the graphite sheets of the graphene conductive film are partially connected, correspondingly, the sheet resistance of the graphene conductive film with 2% by weight of graphene is much higher than that of the graphene conductive film with 1% by weight of graphene Come small.
如c部分所示，並搭配表1，石墨烯導電薄膜的石墨片大部分都開始連接，僅有些許部分的石墨片未連接，相應地，石墨烯3重量%的石墨烯導電薄膜的片電阻遠比石墨烯2重量%的石墨烯導電薄膜來得小。如d部分所示，並搭配表1，石墨烯導電薄膜的石墨片全部連接，相應地，石墨烯3重量%的石墨烯導電薄膜的片電阻為石墨烯1重量%、2重量%、3重量%和4重量%的石墨烯導電薄膜中最小的。因此，隨著石墨烯重量百分濃度上升，石墨片的連續性增加，能形成完整的石墨烯導電薄膜。As shown in part c, and in conjunction with Table 1, most of the graphite sheets of the graphene conductive film are connected, and only some of the graphite sheets are not connected. Correspondingly, the sheet resistance of the graphene conductive film with 3% by weight of graphene Far smaller than the graphene conductive film with 2% by weight of graphene. As shown in part d, and with Table 1, the graphite sheets of the graphene conductive film are all connected, correspondingly, the sheet resistance of the graphene conductive film with 3 wt% of graphene is
請參閱第3圖，其為本發明之石墨烯導電薄膜的拉曼光譜圖。如第3圖所示，分別量測石墨烯1重量%、2重量%、3重量%和4重量%的石墨烯導電薄膜的拉曼光譜，D11峰點~D14峰點為石墨烯的無序振動峰(約為1350cm
-1)，石墨烯之結構缺陷由此判定；G11峰點~G14峰點為石墨烯的主要特徵峰(約為1580cm
-1)，此為碳原子內振動引起，其代表石墨之 sp
2鍵結。2D11峰點~2D14峰點(約為1850 cm
-1~2100cm
-1)，表示石墨烯中碳原子的層間堆疊方式。ID11~ID14為石墨烯1重量%、2重量%、3重量%和4重量%的石墨烯導電薄膜分別於D11峰點~D14峰點的強度，IG11~IG14為石墨烯1重量%、2重量%、3重量%和4重量%的石墨烯導電薄膜分別於G11峰點~G14峰點的強度，ID11/IG11、ID12/IG12、ID13/IG13、ID14/IG14的數值分別為0.92、0.92、0.93、0.93，ID11/IG11、ID12/IG12、ID13/IG13、ID14/IG14的數值皆小於1而表示石墨烯缺陷少，石墨烯導電薄膜品質高。
Please refer to Figure 3, which is a Raman spectrum of the graphene conductive film of the present invention. As shown in Figure 3, the Raman spectra of graphene conductive films with 1% by weight, 2% by weight, 3% by weight and 4% by weight of graphene were measured respectively, and the D11 peak point ~ D14 peak point is the disorder of graphene Vibration peak (about 1350cm -1 ), the structural defect of graphene is judged from this; G11 peak ~ G14 peak is the main characteristic peak of graphene (about 1580cm -1 ), which is caused by the internal vibration of carbon atoms. Represents the sp 2 bonding of graphite. The 2D11 peak point to the 2D14 peak point (approximately 1850 cm -1 ~2100 cm -1 ) indicates the interlayer stacking of carbon atoms in graphene. ID11～ID14 are the intensity of D11 peak point～D14 peak point of the graphene conductive thin film of
請參閱第4圖，其為本發明之石墨烯-奈米碳管導電薄膜的製造流程圖。如第4圖所示，本發明之石墨烯-奈米碳管導電薄膜的製造流程如下：S21步驟：執行微波消化法於奈米碳管以去除其金屬觸媒，並以高溫爐對奈米碳管熱退火(溫度為450度)來去除非晶質碳，取得純化的奈米碳管。Please refer to FIG. 4 , which is a flow chart of manufacturing the graphene-carbon nanotube conductive film of the present invention. As shown in Figure 4, the manufacturing process of the graphene-carbon nanotube conductive film of the present invention is as follows: Step S21: perform microwave digestion on the carbon nanotube to remove its metal catalyst, and treat the nanotube with a high temperature furnace. Thermal annealing of carbon nanotubes (at a temperature of 450 degrees) to remove amorphous carbon and obtain purified carbon nanotubes.
S22步驟：調配石墨烯、奈米碳管、界面活性劑和溶劑；舉例來說，石墨烯可為0.4g，奈米碳管可為0.01-0.03g，界面活性劑可為聚乙烯吡咯烷酮(Polyvinylpyrrolidone, PVP)而其為1-5重量%，溶劑可為乙二醇。S22 step: deploy graphene, carbon nanotubes, surfactant and solvent; For example, graphene can be 0.4g, carbon nanotubes can be 0.01-0.03g, surfactant can be polyvinylpyrrolidone (Polyvinylpyrrolidone , PVP) and it is 1-5% by weight, and the solvent can be ethylene glycol.
S23步驟：利用磁石攪拌機攪拌並混合石墨烯、奈米碳管、界面活性劑和溶劑為石墨烯-奈米碳管導電漿料。Step S23: using a magnetic stirrer to stir and mix the graphene, carbon nanotubes, surfactant and solvent to form a graphene-carbon nanotube conductive paste.
S24步驟：將基板放置於網版印刷機上，將網版對準於基板上，接著利用刮刀取石墨烯-奈米碳管導電漿料並將其塗佈於網板上，使石墨烯-奈米碳管導電漿料附著於基板上，改變網印速度，例如以50-100mm/sec的速度網印石墨烯-奈米碳管導電漿料1-10次，形成石墨烯-奈米碳管導電薄膜於基板上。Step S24: place the substrate on the screen printing machine, align the screen on the substrate, and then use a scraper to take the graphene-carbon nanotube conductive paste and apply it on the screen to make the graphene- The carbon nanotube conductive paste is attached to the substrate, and the screen printing speed is changed, for example, the graphene-carbon nanotube conductive paste is screen-printed 1-10 times at a speed of 50-100mm/sec to form graphene-nanocarbon Tube conductive thin film on the substrate.
S25步驟：將具有石墨烯-奈米碳管導電薄膜的基板，利用烘箱對石墨烯-奈米碳管導電薄膜以80-100度並持續20-30分鐘進行乾燥。Step S25: drying the graphene-carbon nanotube conductive film on the substrate with the graphene-carbon nanotube conductive film in an oven at 80-100 degrees for 20-30 minutes.
S26步驟：乾燥後石墨烯-奈米碳管導電薄膜，利用高溫爐對石墨烯-奈米碳管導電薄膜以350-400度並持續30分鐘進行熱退火。Step S26: After drying the graphene-carbon nanotube conductive film, perform thermal annealing on the graphene-carbon nanotube conductive film at 350-400 degrees for 30 minutes in a high-temperature furnace.
利用本發明之石墨烯-奈米碳管導電薄膜製備方法所製的石墨烯-奈米碳管導電薄膜，奈米碳管的重量百分濃度為0-0.5重量%，界面活性劑的重量百分濃度為1-5重量%。對奈米碳管0重量%、0.1重量%、0.3重量%和0.5重量%的石墨烯-奈米碳管導電薄膜的進行導電性量測，霍爾效應量測儀對不同重量百分濃度的石墨烯-奈米碳管導電薄膜的電阻量測如下表2所示：
請參閱第5圖，其為本發明之石墨烯-奈米碳管導電薄膜的掃描式電子顯微鏡的影像。如第5圖所示，a部分對應奈米碳管0重量%的石墨烯-奈米碳管導電薄膜，b部分對應奈米碳管0.1重量%的石墨烯-奈米碳管導電薄膜，c部分對應奈米碳管0.3重量%的石墨烯-奈米碳管導電薄膜，d部分對應奈米碳管0.5重量%的石墨烯-奈米碳管導電薄膜。如a部分所示，石墨烯-奈米碳管導電薄膜的石墨片全部連接，其與第4圖d部分所示相同。 如b部分所示，並搭配表2，石墨烯-奈米碳管導電薄膜上有少量奈米碳管，相應地，奈米碳管0.1重量%的石墨烯-奈米碳管導電薄膜的片電阻比石墨烯0重量%的石墨烯-奈米碳管導電薄膜來得小。Please refer to FIG. 5, which is a scanning electron microscope image of the graphene-carbon nanotube conductive film of the present invention. As shown in Figure 5, part a corresponds to the graphene-carbon nanotube conductive film of
如c部分和d部分所示，並搭配表2，奈米碳管平均分散於石墨烯-奈米碳管導電薄膜，石墨片上的奈米碳管有良好的分散性，隨著奈米碳管的重量百分濃度上升，石墨烯-奈米碳管導電薄膜的片電阻下降，其原因是石墨烯的電傳導方向為橫向傳輸，奈米碳管電傳導為縱向傳輸而會受限於每根奈米碳管間不連續所造成的接面電阻，結合石墨烯和奈米碳管可使片電阻的數值下降。As shown in parts c and d, and with Table 2, the carbon nanotubes are evenly dispersed in the graphene-carbon nanotube conductive film, and the carbon nanotubes on the graphite sheet have good dispersion. The weight percentage concentration increases, and the sheet resistance of the graphene-carbon nanotube conductive film decreases. The junction resistance caused by discontinuity between carbon nanotubes, combining graphene and carbon nanotubes can reduce the value of sheet resistance.
請參閱第6圖，其為本發明之石墨烯-奈米碳管導電薄膜的拉曼光譜圖。如第6圖所示，分別量測奈米碳管0重量%、0.1重量%、0.3重量%和0.5重量%的石墨烯-奈米碳管導電薄膜的拉曼光譜，D21峰點~D24峰點為石墨烯的無序振動峰(約為1350cm -1)，石墨烯之結構缺陷由此判定；G21峰點~G24峰點為石墨烯的主要特徵峰(約為1580cm -1)，此為碳原子內振動引起，其代表石墨之 sp 2鍵結。2D21峰點~2D24峰點(約為1850 cm -1~2100cm -1)，表示石墨烯中碳原子的層間堆疊方式。在奈米碳管0重量%的石墨烯-奈米碳管導電薄膜的拉曼光譜，在1350cm -1有些微D波段產生。ID21~ID24為奈米碳管0重量%、0.1重量%、0.3重量%和0.5重量%的石墨烯-奈米碳管導電薄膜分別於D21峰點~D24峰點的強度，IG21~IG24為奈米碳管0重量%、0.1重量%、0.3重量%和0.5重量%的石墨烯-奈米碳管導電薄膜分別於G11峰點~G14峰點的強度，ID21/IG21、ID22/IG22、ID23/IG23、ID24/IG24的數值分別為0.93、0.99、0.99、0.99，ID21/IG21、ID22/IG22、ID23/IG23、ID24/IG24的數值皆小於1而表示石墨烯-奈米碳管缺陷少，石墨烯-奈米碳管導電薄膜品質高。 Please refer to FIG. 6, which is a Raman spectrum of the graphene-carbon nanotube conductive thin film of the present invention. As shown in Figure 6, the Raman spectra of the graphene-carbon nanotube conductive films of 0 wt%, 0.1 wt%, 0.3 wt% and 0.5 wt% of carbon nanotubes were measured respectively, D21 peak point ~ D24 peak The point is the disordered vibration peak of graphene (about 1350cm -1 ), and the structural defects of graphene are judged from this; the G21 peak ~ G24 peak is the main characteristic peak of graphene (about 1580cm -1 ), which is Induced by vibrations within carbon atoms, which represent the sp 2 bonding of graphite. The 2D21 peak point to the 2D24 peak point (approximately 1850 cm -1 ~2100 cm -1 ) indicates the interlayer stacking of carbon atoms in graphene. In the Raman spectrum of the graphene-carbon nanotube conductive film with 0 wt% carbon nanotubes, there is a slight D-band at 1350 cm -1 . ID21～ID24 are the intensity of D21 peak point～D24 peak point respectively in the graphene-carbon nanotube conductive film of 0 weight %, 0.1 weight %, 0.3 weight % and 0.5 weight % of carbon nanotubes, and IG21～IG24 is nanometer The graphene-carbon nanotube conductive films of 0 wt%, 0.1 wt%, 0.3 wt% and 0.5 wt% of carbon nanotubes are respectively at the intensity of G11 peak point ~G14 peak point, ID21/IG21, ID22/IG22, ID23/ The values of IG23, ID24/IG24 are 0.93, 0.99, 0.99, 0.99 respectively, and the values of ID21/IG21, ID22/IG22, ID23/IG23, ID24/IG24 are all less than 1, which means that there are few defects in graphene-carbon nanotubes, graphite The ene-carbon nanotube conductive film is of high quality.
承上所述，本發明之石墨烯導電薄膜和其製備方法，利用界面活性劑的添加和乾燥、熱退火製程的搭配，使石墨烯導電薄膜的片電阻下降而導電率提高。Based on the above, the graphene conductive film and its preparation method of the present invention use the addition of surfactants and the combination of drying and thermal annealing processes to reduce the sheet resistance of the graphene conductive film and increase the conductivity.
承上所述，本發明之石墨烯-奈米碳管導電薄膜，利用界面活性劑和奈米碳管的添加和乾燥、熱退火製程的搭配，使石墨烯-奈米碳管導電薄膜的片電阻下降而導電率提高，且製備方法容易，而能應用於低成本電子元件。As mentioned above, the graphene-carbon nanotube conductive film of the present invention utilizes the addition of surfactant and carbon nanotube and the combination of drying and thermal annealing process to make the sheet of graphene-carbon nanotube conductive film The resistance decreases while the conductivity increases, and the preparation method is easy, so it can be applied to low-cost electronic components.
以上所述僅為舉例性，而非為限制性者。任何未脫離本發明之精神與範疇，而對其進行之等效修改或變更，均應包含於後附之申請專利範圍中。The above descriptions are illustrative only, not restrictive. Any equivalent modification or change made without departing from the spirit and scope of the present invention shall be included in the scope of the appended patent application.
S11~S16、S21~S26:步驟 D11~D14、D21~D24、 G11~G14、G21~G24、2D11~2D14、2D21~2D24:峰點 S11~S16, S21~S26: steps D11~D14, D21~D24, G11~G14, G21~G24, 2D11~2D14, 2D21~2D24: peak point
第1圖為本發明之石墨烯導電薄膜的製造流程圖。 第2圖為本發明之石墨烯導電薄膜的掃描式電子顯微鏡的影像。 第3圖為本發明之石墨烯導電薄膜的拉曼光譜圖。 第4圖為本發明之石墨烯-奈米碳管導電薄膜的製造流程圖。 第5圖為本發明之石墨烯-奈米碳管導電薄膜的掃描式電子顯微鏡的影像。 第6圖為本發明之石墨烯-奈米碳管導電薄膜的拉曼光譜圖。 Fig. 1 is a manufacturing flow chart of the graphene conductive film of the present invention. Figure 2 is a scanning electron microscope image of the graphene conductive film of the present invention. Fig. 3 is a Raman spectrum of the graphene conductive thin film of the present invention. Fig. 4 is a manufacturing flow chart of the graphene-carbon nanotube conductive film of the present invention. Fig. 5 is a scanning electron microscope image of the graphene-carbon nanotube conductive thin film of the present invention. Fig. 6 is a Raman spectrogram of the graphene-carbon nanotube conductive thin film of the present invention.
S11~S16:步驟 S11~S16: Steps
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